Transforming Plastics to Single Atom Catalysts for Peroxymonosulfate Activation: Axial Chloride Coordination Intensified Electron Transfer Pathway

Abstract Transforming plastics into single‐atom catalysts is a promising strategy for upcycling waste plastics into value‐added functional materials. Herein, a graphene‐based single‐atom catalyst with atomically dispersed FeN4Cl sites (Fe─N/Cl─C) is produced from high‐density polyethylene wastes via one‐pot catalytic pyrolysis. The Fe─N/Cl─C catalyst exhibited much higher turnover frequency and surface area normalized activity (Kac) compared with the Fe─N─C catalyst without axial Cl modulation. Both experiments and density functional theory (DFT) computations demonstrated that the axial incorporation of chloride fine‐tuned the coordination environment of FeN4 sites and enhanced peroxymonosulfate (PMS) activation because of improved conductivity and modulated spin state. In situ, Raman, and infrared spectroscopic techniques revealed that PMS is activated by the Fe─N/Cl─C catalyst through an electron transfer process. The formation of a key PMS* intermediate at the Fe site effectively elevated the redox capacity of the catalyst surface to realize a fast degradation of diverse pollutants. The non‐radical oxidation manner secures high selectivity toward target pollutants and high chemical utilization efficiency. A continuous operation in a column reactor also demonstrated the high efficiency and stability of the (Fe─N/Cl─C + PMS) system for practical water treatment.